Bis-triazinylamino stilbene compounds



effectively brightened. As however, the 4.4-bis-triazi;nyl-

2,762,891 Patented Sept. 11, 1956 United States Patent C ice of fluorescence light and the substantivity of the compound under the conditions in which it is used.

It has now been found that new bis-triazinylamino stilbene compounds which dissolve well in water, have an intensive. blue fluorescence and very good affinity to cellulose and. which are distinguished by an improved maximal brightening on cellulose fibres are obtained if N Drawlllgl P November the known condensation products from 1 mol of 4.4'-di- Sena] 471,073 aminostilbene-2.2'-disulphonic acid and 2 mols of cy- Claims priority, application switzgrland l0 anuric halide or the aqueous solution of their salts are N b 26, .1953 condensed with 2 mols of a primary aromatic amine of the. benzene series which may contain non-ionogenic ring 5 260-2495) substituents and' with 2 mols of the secondary N-methyl or N-ethyl ethanolamine. The condensation is per- The present invention is concerned with blue fiuoresformed in steps, in any Order desired, and in the Presence cing bis-triazinylamino stilbene compounds having good of agents: which neutralise the mineral acid, but must be water solubility which, because of their good atlinity to so performed that symmetrical compounds of the gencellulose and their high intensity of fluorescence, have eral formula:

areobtained. In this formula R represents an aliphatic hydrocarbon radical with 1 to 2 carbon atoms and A represents a phenyl radical, if desired non-ionogenically further substituted-preferably by chlorine, alkyl or alkoxy groups.

The condensation of the 4.4'-bis-[4.6-dihalogen-l.3.5-

triazinyl-(2)-amino]-stilbene-2.2'-disulphonic acids can be performed in an aqueous solution of the alkali metal salts by known methods at 10-50 C. in the first step and at 90-100 C. in the second step. Aminobenzene, 2- and stituted in the triazine rings by at leastone and'preferably Particularly Y two amino groups which may be organically substituted, benzene, 0r and Particularly Y- have attained a great importance due to their violetblue b n Zethoxydcminobenzene, -p y-1- min0- 'to blue fluorescence and their good afiinity to cellulose bBnZene, dimethylaminobenzefle, 3 m yas optical brightening agents in the textile and paper in- 4rmethyl'l-aminobenzene eXample can used as dustries as well as for laundering purposes in the house- P y aromatic amines 0f the benzene Series- I is hold. Today, according to the intended use, very definite advantageous first to condense 2 H1018 0f the ar ati demands are made of these compounds with regard to amine at 10-50 C. in the presence of the necessary water solubility, aflinity to the fibre, shade of fluorescence amount of sodium acetate, sodium bicarbonate or sodium light, wet fastness on the fibre, etc. The soap-saving carbonate as agent neutralising the mineral acid and then textile. finishing tr for example r s e y subto condense 2 molsof the aliphatic amine at 90 10o c. stantive brightening agents which have good watersoluin which condensation an excess of amine can be used bility and good wet fastness, the soap and washing agents 60 as acid binding agent. industry on the other hand requires such optical brighten,- The. new compounds are obtained in the form of their ing agents as additives to the washing agents for use-in more or less yellow coloured alkali salts which can be the household wash which, on repeated use, will not uneasily isolated. After drying they have relatively good desirably discolour the textiles. Always however, is the Water solubility, a good affinity to cellulosefibres in greatest possible maximal brightening desired so that aqueous and also in alkaline solutions containing soaps also the more, strongly yellow coloured goods can be or detergents and they have an improved bleaching elfect compared with the comparable monoethanolamine, diamino stilbene-2'.2-disulphonic acids have a yellow self ethanolamine and morpholine compounds. In addition colour, on increasing the concentration on the fibre in they have better water solubility than the last above named orderto compensate a stronger yellow tinge in thegoods compounds. Due to the solubility they can be put to in daylight by theblue fluorescence light, a point is-soon good use both in the textile finishing industry as well. as reached where the yellow ,selfcolour of the agent bein the manufacture of washing agents. comes visible thus making it'irnpo i le 0 increase. the Thev following examples illustrate the invention withwhite content. The maximal brightening etfect of such out limiting it in any way. Parts are given as parts by a water soluble optical brightening agent which can be weight and the temperatures are in degrees centigrade. obta n d for agi e am u t s s anse en d t Example 1 n. re e se r tio o i s s lf ol u nd. is: ep nde t in direct ratio on the intensity of fluorescence, the-shade 18. 5 parts, of: cyanurrc. chloride are dissolved in 2,7 62,801 BIS-TRTAZINYLAMINO STILBENE COMPOUNDS Heinrich Hiiusermann, Basel, Switzerland, assig nor to 5 J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm CHPCHr-OH an improved maximal brightening effect. It is also concerned with a process for the production thereof. 'In addition, it is concerned with the use of such compounds for the optical brightening of cellulose in the form of fibres, textiles, household linen and paper, the production and use of washing and cleaning agents which contain the compounds according to the invention as optical brightening agents as well as the attainment of cellulose material brightened with the aid of these compounds and the material so brightened.

4.4'-bis-triazinylamino stilbene-2.2-disulphonic acids or the water soluble salts thereof which are further'subparts of acetone and the solution is added to a mixture of 200 parts of ice and 200 parts of water. The cyanurio chloride suspension so obtained is reacted while stirring in the usual way with a pH value of 5.6 at -5 with a solution of 20.7 parts of the sodium salt of 4.4 diaminostilbene-2.2-disulphonic acid in 200 parts of water and a solution of 5.3 parts of sodium carbonate. The solution of the sodium salt of 4.4-bis-[4.6-dichloro-1.3.5-triazinyl- (2)-aminol-stilbene-2.2-disulphonic acid is stirred at 15- 25 with 9.3 parts of aniline and the pH value is kept between 6.5 and 7.5 by the slow addition of a solution of 5.3 parts of sodium carbonate in 25 parts of water. After no more aniline can be traced, so much N-methylethanolamine is added dropwise until the reaction mixture turns phenolphthalein paper red whereupon the mixture is gradually heated to 90-95 and stirred for 1 /2 hours at this temperature, the reaction being kept always phenolphthalein alkaline with N-methylmonoethanolamine. In all, 15-20 parts of N-methylethanolamine are needed. While heating, the acetone is distilled oil through a sloping condenser. The resulting sodium salt of 4.4-bis- [4 phenylamino-6-(fi-hydroxyethylmethylamino)-1.3.5- niazinyl-(2)-amino]-stilbene-2.2-disulphonic acid is separated by salting out with 75 parts of sodium chloride. The product is washed with 5% sodium chloride solution and dried in the vacuum at 7090. The new stilbene compound forms a yellowish powder which is soluble in water. An aqueous solution of the product has a blue fluorescence in daylight.

If cellulose materials which appear colourless'to weakly yellowish are treated with such an aqueous solution, then the materials so treated appear to be much lighter than before the treatment. Dueto its high maximal brightening, the product is particularly suitable for textile finish- If in the above example, 10.7 parts of o-toluidine, 10.7 parts of m-toluidine, 12.75 parts of m-chloraniline, 12.3 parts of rn-anisi'dine, 12.3 parts of o-anisidine or 12.1 parts of p-xylidine are used instead of 9.3 parts of aniline, then compounds with very similar properties are obtained.

Example 2 18 parts of N-ethyl-monoethanolamine are added over 30 minutes at 5-10" to 71 parts of the sodium salt of 4.4 bis-[4.6-dichloro-1.3.S-triazinyl-(Z) -amino]-stilbene- 2.2'-disulphonic acid in 1500 parts of water.- The mixture 'is stirred for 5 hours at 30-40 and the reaction is kept" weakly alkaline to brilliant yellow paper by the slow addition dropwise of a solution of 11 parts of sodium carbonate in 50 parts of water. 24.6 parts of p-methoxy aniline are then added and the temperature is raised to 90-95"; The mixture is stirred for 4 hours at this temperature and the reaction is kept neutral to litmus paper with 15% sodium carbonate solution. Finally so much sodium carbonate solution 15% is added until the mixture becomes alkaline to phenolphthalein. The product is then salted out with 150 parts of sodium chloride, and, after washing with 5% salt solution, it is dried at 70-90 in the vacuum. The disodium salt of 4.4-bis-[4-(pmethoxyphenylamino) -6- (N-ethyl-fihydroxyethylamino) 1.3.5-triazinyl-(2)-amino]-stilbene-2.2'-disulphonic acid is so obtained as a yellowish water soluble powder. In aqueous solution the compound has a blue and in alcoholic solution a violet fluorescence in daylight. This compound is excellently suitable as an additive to washing'liquors for white wash.

Somewhat stronger but more redly fluorescing products are obtained'if in this example the 24.6 parts of p-anisidine are replaced by 18.6 parts of aniline, 24.6 parts of m-anisidine or 26' parts of m-phenetidin'e. The latter compounds are specially suitable for textile finishing.

Example 3 dissolved in 1500 parts of water are stirred well at 15-25 with v27.4 parts of 3-methoxy-4-methylaniline until the amine disappears. The liberated hydrochloric acid is continually neutralised by the gradual addition of a solution of 10.6 parts of calcinated sodium carbonate in parts of water. When no more amine can be traced, 18 parts of N-methyl-monoethanolamine are added, the mixture is slowly heated to 90-95 and stirred at this temperature for 1 /2 hours. The reaction is kept always weakly phenolphthalein alkaline by the addition of a 15% sodium carbonate solution. The reaction product is isolated as described in Examples 1 and 2, washed and dried. The disodium salt of 4.4-bis-[4-(3-methoxy-4-methylphenylamino) 6 (N methyl-,8-hydroxyethylamino)-1.3.5- triazinyl-(2)amino]-stilbene-2.2-disulphonic acid is obtained as a yellowish water soluble powder. The product has similar properties to those of the compounds obtained according to Example 1.

Very valuable products are also obtained if in this example the 27.4 parts of 3-methoxy-4-methyl aniline are replaced by 28.3 parts of 3-chloro-4-methyl aniline or by 28.3 parts of 3-chloro-2-methyl aniline.

Example 4 A solution of 15.95 parts of p-anisidine chlorohydrate is added in the course of over one hour at 15-20 while stirring well to 35.5 parts of the disodium salt of 4.4'-bis- [4.6 dichloro 1.3.5-triazinyl-(2)-amino]-stilbene-2.2'- disulphonic acid in 1000 parts of water. The hydrochloric acid which is liberated is neutralised by the addition of a 15% sodium carbonate solution. The pale yellowish suspension is then stirred at 25-35 the reaction being kept neutral to litmus paper, until no free p-anisidine can be traced. 64 parts by volume of 15 sodium carbonate solution are needed. 9 parts of N-methylmonoethanol amine are then added and the reaction mixture is condensed for 1 /2 hours at 90-95 as described in Example 3, the reaction being kept weakly phenolphthalein alkaline. By salting out, washing and drying, the sodium salt of 4.4'-bis-[4-(p-methoxy-phenylamino)- 6 (N methyl-13-hydroxyethylamino)-1.3.5-triazinyl-(2)- amino]-stilbene-2.2'disulphonic acid is obtained as a yellow water soluble powder. This product, because of its neutral white nuance, is excellently suitable as a brightening agent in washing liquors for white wash.

Compounds with similar properties are obtained if in this example the 15.95 parts of p-anisidine-chlorohydrate are replaced by 22.15 parts of p-aminodiphenyl ether chlorohydrate or 17.35 parts of o-phenetidine chlorohydrate.

Example 5 Example 6 White cotton poplin'is treated for 15 minutes at 40 in a bath (liquor ratio 1:30) containing 0.005 g. of the sodium salt of 4.4-bis-[4-phenylarnino-6 -(fi-hydroxyethylmethylamino) 1.3.5 triazinyl (2) amino]- stilbene-2.2-disulphonic acid obtained according to Ex ample 1, and 2 g. of Glaubers salt per litre. After rinsing and drying, the material so treated has a much whiter appearance in daylight than before treatment.

Example 7 p 1 part of white wash such as, e. g. pillow cases, sheets, etc. are boiled for 30 minutes in l O-parts of a washing liquor which contains per litre 8 g. of one of the usual 5 soap and perborate washing agents, which agent con- 2. The bis-triazinylamino-stilbene compound having tains 0.03% of the sodium salt of 4.4'-bis-[4-(p-meththe formula:

OH-CHg-CE: /CH:CH:OH

OH NHQCH=CH3NH- N O-HN $0.11 03H NEG oxyphenylamino) 6 9 hydroxyethyl methylamino)- 3. The bis-triazinylamino-stilbene compound having l.3.5-triazinyl-(2)-amino]-stilbene-2.2-.disulphonic; acid the formula:

OH-CHz-CH: /CH|-CHs-OH obtained according to Example 4. The goods are then rinsed and dried. A dazzling white wash which has no 4. The bis-triazinylamino-stilbene compound having unpleasant reddish tinge is obtained. the formula:

Ho0H:-01 1, /CHCH:OH

N N H c CH -NHQ0H=0HQNH- N Q11: 01H 0,11 NHQ OH; OCH:

-5. The bis-triazinylamino-stilbene compound having the formula:

HO-OHg-CH, CHI-OHjOH 1. A bis-triazinylamino-stilbene compound which corresponds to the formula:

HO-CHz-CH; CH -CHg-OH N N H30 NH OH=CH NH- \I A-HN 0m SOH H-A wherein A stands for a member selected from the group consisting of 55 O References Cited in the file of this patent UNITED STATES PATENTS Q 2,667,458 Williams I an. 26, 1954 60 FOREIGN PATENTS 502,807 Belgium 1951 0H,0C 624,052 Great Britain 1949 and g5 

1. A BIS-TRIAZINYLAMINO-STILBENE COMPOUND WHICH CORRESPONSE TO THE FORMULA: 